The present invention relates to a cation exchange membrane which is useful for concentration or separation of an aqueous electrolyte solution or for production of demineralized water employing an ion exchange membrane, and a method for its production. More particularly, it relates to a cation exchange membrane selectively permeable to monovalent cations, which permits cations having small electric charges to readily permeate particularly selectively, and which is useful for concentration or separation of an aqueous electrolyte solution or production of demineralized water, by electrodialysis, and a method for its production.
Concentration or separation of an aqueous electrolyte solution, or production of demineralized water, employing an ion exchange membrane, is carried out in various fields. Especially in Japan, in order to establish a salt production technique of concentrating seawater by electrodialysis, many membranes selectively permeable to monovalent ions, which are capable of selectively concentrating sodium chloride from various seawater components, have been proposed and are being practically used. Further, their applications to areas other than concentration of seawater, have also been attempted.
The following methods may be mentioned as conventional methods for imparting selective permeability to monovalent cations, to cation exchange membranes.
(1) A method of making the surface portion of a cation exchange membrane to have a dense structure (for example, making the surface layer to be a layer having a high cross-linking degree or a layer having a high fixed ion concentration);
(2) A method of forming an electrically neutral thin layer containing no ion exchange groups, on the surface of a cation exchange membrane;
(3) A method of forming a thin layer having an opposite electrical charge, on the surface of a cation exchange membrane.
(4) A method of employing two or more of the above methods (1) to (3) in combination.
Among the above methods, method (1) is usually excellent in durability, but has a drawback that the electrical resistance is high, and method (2) is inadequate in selective permeability. Whereas, method (3) usually has a merit in that selectivity to monovalent ions is excellent, and the electrical resistance is low, but the initially proposed method (JP-704599) had drawbacks that the molecular weight of the material forming the opposite electric charge layer was low, the durability of the selectivity to monovalent cations was inadequate, and if the opposite electrical charge layer was made to increase the durability or the selectivity, an increase in the direct current resistance or a decrease in the limiting current density was likely to be led.
Many proposals have been made to overcome such drawbacks, and one of such proposals is a method of forming a selective layer by an opposite electrical charge compound having the solubility controlled, such as a non-crosslinkable substance having anion exchange groups and having a specific HLB value and molecular weight (JP-A-55-8838) or a polymer having anion exchange groups and having a specific solubility to seawater (JP-A-9-48861). By such a method, the durability under application of electric current can be improved, but there is a problem that in a state where application of electric current has been stopped, the selective layer tends to gradually elute from the membrane, whereby the selectivity tends to deteriorate.
Further, as a method to prevent such a drawback, a method of treating a cation exchange membrane immersed in a mixture of an organic solvent and water, with the opposite electrical charge compound (JP-B-6-49786), or a method of treating it with a high molecular amine in an electrically non-charged state (JP-A-4-90828) for the purpose of improving the durability by permitting the opposite electrical charge layer to penetrate into the membrane, but such a method has not necessarily been adequate.
Further, there is a method in which a compound having an opposite electrical charge or convertible to have an opposite electrical charge, is polymerized on the surface of a cation exchange membrane to form an insolubilized layer (JP-A-62-205135, etc.). By this method, the durability of the selectivity to monovalent cations can be improved to a large extent, but there is a problem such that the direct current resistance of the membrane is likely to be high at the time of concentration of seawater, while the alternate current resistance of the membrane is low.
The present invention has been made to solve the above problems, and the cation exchange membrane selectively permeable to monovalent cations of the present invention, is characterized by having, on at least one side of the cation exchange membrane, a surface treated by contact with high molecular cations in the presence of anions of an oxyacid or ions of an organic sulfonic acid.
Further, the method for producing a cation exchange membrane selectively permeable to monovalent cations of the present invention, is characterized by contacting at least one surface of a cation exchange membrane with high molecular cations in the presence of anions of an oxyacid and ions of an organic sulfonic acid (hereinafter, these acids may sometimes be referred to as an oxyacid, etc., and their ions may sometimes be referred to as oxyacid anions, etc.).
In the present invention, as described above, at least one surface of the cation exchange membrane is brought in contact with high molecular cations in the presence of anions of an oxyacid or ions of an organic sulfonic acid. However, the reason why such a contact is effective, has not yet been clarified, but the effects are evident from Examples given hereinafter.
The cation exchange membrane selectively permeable to monovalent cations of the present invention is one having, on at least one side of the cation exchange membrane, a surface treated by contact with high molecular cations in the presence of anions of an oxyacid or ions of an organic sulfonic acid, as mentioned above. As cation exchange membranes prior to the treatment to impart the selective permeability to monovalent cations, the following membranes may, for example, be mentioned, and they can be used without any particular restriction.
(1) A cation exchange membrane obtained by impregnating a reinforcing cloth with styrene/divinyl benzene, followed by polymerization and then by sulfonization.
(2) A heterogeneous cation exchange membrane formed in a membrane-shape from a kneaded blend of a cation exchange resin powder and a binder.
(3) A cation exchange membrane obtained by graft-polymerizing a monomer convertible to a cation exchange group or having a cation exchange group to a polyolefin or fluorine type film.
(4) A perfluoro type cation exchange membrane useful as a sodium chloride electrolytic membrane for an ion exchange membrane method.
To prepare the cation exchange membrane selectively permeable to monovalent cations of the present invention, at least one side of a cation exchange membrane as listed above, is contacted with high molecular cations in the presence of anions of an oxyacid or ions of an organic sulfonic acid. The high molecular cations in the present invention are defined to be a high molecular electrolyte, of which the average molecular weight (the average formula weight) of cations charged positively during the use of the cation exchange membrane, is at least 5,000. As the high molecular electrolyte which gives such high molecular cations, a water-soluble polymer may, for example, be mentioned, such as polyethyleneimine, polyallylamine, a polyamizine, a hexamethylenediamine/epichlorohydrin polycondensate, a dicyandiamide/formalin polycondensate, a guanidine/formalin polycondensate, a polyvinyl benzyl trimethylammonium chloride, a poly(4-vinyl pyridine), a poly(2-vinyl pyridine), a poly(dimethylaminoethyl acrylate), a poly(dimethylaminoethyl methacrylate), a poly(1-vinyl imidazole), a poly(2-vinyl pyrazine), a poly(4-butenyl pyridine), a poly(N,N-dimethylacrylamide), a poly(N,N-dimethylaminopropylacrylamide), or a salt thereof.
Among them, a homopolymer or copolymer of allylamine having a molecular weight of at least 5,000, is particularly preferred. Specifically, a polyallylamine having a molecular weight of at least 5,000, preferably at least 10,000, particularly preferably at least 50,000, as a homopolymer of allylamine, or a copolymer of allylamine with other monomer, such as a copolymer of allylamine with diallylamine, is particularly preferred, in that it provides a remarkable effect for imparting selective permeability to monovalent cations by the treatment by contact with the cation exchange membrane in the presence of anions of an oxyacid according to the present invention.
Now, the anions to be present together with the above-described high molecular cations in the present invention, will be described. As mentioned above, they include anions of an oxyacid and ions of an organic sulfonic acid. The anions of an oxyacid as the former, are anions which will be formed when an oxyacid having oxygen coordinated to a metal or non-metal other than oxygen, or its salt, is dissolved in water.
The compound which forms such anions of an oxyacid, may, for example, be nitric acid, nitrous acid, sulfuric acid, sulfurous acid, pyrosulfuric acid, carbonic acid phosphoric acid, silicic acid, chloric acid, chromic acid, antimonic acid, manganic acid, or a salt thereof. Among them, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, pyrosulfuric acid, carbonic acid phosphoric acid, silicic acid, or a salt thereof, is further preferred. The salt of such an acid may, for example, be a salt of an alkali metal or an alkaline earth metal.
Further, the latter ions of an organic sulfonic acid are anions which will be formed when a sulfonic acid having a sulfonic group bonded to an aromatic ring such as a benzene ring, to an alkylene group directly bonded to an aromatic ring or to a carbon atom of an aliphatic hydrocarbon, or its salt, is dissolved in water. The compound which forms such anions may, for example, be a polystyrene sulfonic acid or its salt, a polyvinyl benzyl sulfonic acid or its salt, or a polyvinyl sulfonic acid or its salt.
The above-mentioned high molecular electrolyte which forms high molecular cations, is contacted to one side or both sides of a cation exchange membrane in the presence of such a compound which forms anions of an oxyacid. It is preferred from the viewpoint of development of selective permeability to monovalent cations and its durability that the anions of an oxyacid are present in an amount of at least 0.5 chemical equivalent to the high molecular cations. Further, anions other than the anions of an oxyacid, such as chlorine ions, may also be present without any particular problem.
The method for the treatment is not particularly limited, and various methods are available, such as a method wherein a solution obtained by preliminarily mixing a high molecular electrolyte solution and a solution of an oxyacid or the like, or a salt thereof, is coated or impregnated on at least one side of a cation exchange membrane, and a method wherein either one of the solutions is coated or impregnated to a cation exchange membrane and then the other solution is coated or impregnated, to let both be present on the cation exchange membrane.
With respect to the solution of a high molecular weight electrolyte to be coated or impregnated to the cation exchange membrane, the concentration varies depending upon the time or temperature for the contact. However, it is contacted usually at a concentration of from 0.01 to 200,000 ppm, preferably from 0.2 to 5,000 ppm at a temperature of from 0 to 150xc2x0 C., preferably from 20 to 120xc2x0 C.
Thus, the selectivity to monovalent cations will be imparted by the contact in the presence of the anions of an oxyacid and high molecular weight cations. After such treatment, post treatment may further be carried out such as heat treatment or a reaction with formalin, epichlorohydrin or an alkylene dihalide utilizing reaction sites in the high molecular cations, such as active hydrogen bonded to a nitrogen atom, for insolubilization.
In the following, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples, and it should be understood as defined by the description in the claims.
Before describing the Examples, the evaluation method for the cation exchange membrane selectively permeable to monovalent cations will firstly be explained. For this evaluation, a four compartment type batch system electrodialytic cell comprising an anode compartment, a dilution compartment, a concentration compartment and a cathode compartment, having an effective current-carrying area of 4xc3x972.5 cm2, defined by disposing, from the side of an anode employing a silver/silver chloride electrode, an anion exchange membrane selectively permeable to monovalent anions, a cation exchange membrane as an Example of the present invention, and an anion exchange membrane selectively permeable to monovalent anions, was formed, and such a cell was used.
To the anode compartment, the concentration compartment and the cathode compartment of such an electrodialytic cell, 1 mol/l of a NaCl solution was supplied, and to the dilution compartment, a solution containing 0.45 mol/l of chloride ions, 0.025 mol/l of sulfuric acid ions, 0.37 mol/l of sodium ions, 0.01 mol/l of potassium ions, 0.05 mol/l of magnesium ions and 0.01 mol/l of calcium ions, was filled, whereupon electrodialysis was carried out at 25xc2x0 C. at a current density of 2 A/dm2, whereupon from the amounts of magnesium ions, calcium ions and chloride ions concentrated in the concentration compartment, a simplified salt purity ratio was obtained by the following formula.
Here, the simplified salt purity ratio is a numerical value representing the performance for selectively concentrating NaCl from seawater, and the higher the simplified salt purity ratio, the higher the selectivity. In the following formula, (xe2x88x922.5) at the end represents the proportion of K ions in the seawater ions empirically obtained. In this simplified salt purity ratio, the concentration of K ions is not measured, and the content of K ions is corrected by subtracting the above empirical value.
Simplified salt purity ratio (%)=100xc3x97(([Cl]xe2x88x92[Mg]xe2x88x92[Ca])/[Cl])xe2x88x922.5
And, the cation exchange membrane of the Example and SELEMION ASV as an anion exchange membrane manufactured by Asahi Glass Company, Limited, were set in an electrodialyzer 0 (zero) model (effective area: 2.1 dm2), manufactured by Asahi Glass Company, Limited, and a concentration test was also carried out wherein real seawater was supplied to the dilution compartment at a flow rate of 7 cm/sec at a temperature of 25xc2x0 C. Except for the cation exchange membrane, the unit cell voltage was obtained under the same conditions. Further, the current density was varied, and the voltage was measured, whereby the current density at which the direct resistance increased, was obtained as the limiting current density.